— i5° — 



^CH-CH 2 



C-CH, \CH.C(CH,) 2 0H -> 

 CH- CH 2 



/CHg-CE, 



HO.C.CH3 \CH-C(CH 8 ) 2 0H 



^CH-CH 2 



a - Terpineol 



Terpin 



It was remarkable that at the time, in the first conversion with 

 CH 3 MgI, only a comparatively small yield was obtained. Recent 

 experiments by the same authors 1 ) now show clearly that the bad yield 

 is due to the fact that, besides the CO-group, also simultaneously the 

 carboxethyl-group enters into action with Grignard's reagent; from 

 the body thus produced, 



/CH 2 -CH 2 



IMgO-C-CHg \cH.C(CH 3 ). 2 OMgI 



X CH 2 -CH 2 



there is also easily formed cis-terpinhydrate of the m. p. 107 . The 

 synthesis of this product, which was obtained in a quantity of at 

 most 7 g. from 50 g. ketonic acid ester, is therefore greatly simplified 

 by this secondary reaction. 



Linalool. Roure Bertrand Fils 2 ) believe that the question, 

 whether linalool is really a tertiary alcohol or not, has been finally 

 solved by them by a comparative study of the esterification of linalool 

 and geraniol. The two alcohols were submitted to esterification with 

 glacial acetic acid, for which 6 mol. acetic acid were used to 1 mol. 

 of the two carbinols. The mixtures were left standing in a room 

 which was but little subject to fluctuations of temperature. The progress 

 of the esterification was ascertained by determining the ester-content 

 of several samples. 

 After 24 hours there were formed, in parallel tests, 5,5% geranyl acetate 



but only 0,4 °/ linalyl acetate; 

 after 10 days, 29,2 °/ geranyl acetate, but only 0,6 °/ linalyl acetate, 



jj 24 » 45>o /o » » » " *>* /o » " 



5 months, 85,6 °/ „ „ „ „ 3,9% „ 



>j 12 „ 90,0 /o ?j jj j> ?) 5>3 /o " " 



For geraniol this result corresponds to that which might be expected 

 in the case of a primary alcohol; the extremely slow progress of 

 the esterification in linalool, however, appears to be only possible with 

 a tertiary alcohol. 



With regard to the determination ofhydroxyl groups according 

 to Zerewitinoff, and of linalool according to Boulez, see under 

 Analytical Notes, p. 117 and 119. 



x ) Journ. chem. Soc. 91 (1907), 372. 



2 ) Bericht Roure-Bertrand Fils, April 1907, 1. 



